Abstract
Malonaldehyde (M), a product of polyunsaturated fatty acid oxidation, reacted with the sulfhydryl as well as with the amino groups of cysteine (cys). The cys-M product had an absorption maximum at 310 mµ, and the extinction coefficient at pH 7.0 was 2.3 × 104. Elementary analysis of the cys-M product agreed with a structure in which 2 moles of cysteine had reacted with 3 moles of malonaldehyde. The molecular weight of cys-M preparations increased on storage and the UV absorption changed from 310 to 315–320 mµ, with a consequent shift to longer wavelength in the visible.
Methionine (meth) reacted with malonaldehyde under the same reaction conditions only at the α-amino group, similar to glycine (gly). The apparent pKa of the carboxyl group of gly-M increased to 3.36 and that of meth-M to 3.19, representing an increase of about one pKa unit over the natural amino acids. For gly-M and meth-M the respective absorption maxima were 272 and 282 mµ. The spectral shifts from 267 to 315 mµ of the amino acid-M products with respect to β-oxyacrolein were explained in terms of increasing substitution at the β-carbon of the α,β-unsaturated carbonyl system. When the α-amino-malonaldehyde condensation products of methionine and glycine reacted with semicarbazide the original amino acids and disemicarbazone of malonaldehyde were formed.
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Buttkus, H. Reaction of cysteine and methionine with malonaldehyde. J Am Oil Chem Soc 46, 88–93 (1969). https://doi.org/10.1007/BF02541215
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DOI: https://doi.org/10.1007/BF02541215